Synthesis of 6-deoxy-5-thio-d-glucose

Three routes were investigated for the conversion of d-glucose into the title compound. In the first approach, reduction of the 5,6-thürane ring of 5,6-dideoxy-5,6-epithio-1,2-O-isopropylidene α-d-glucofuranose (17) as well as that of its 3-O-allyl derivative (13) with lithium aluminium hydride was investigated; 17 afforded the corresponding 6-deoxy derivative besides di-, tri-, and poly-mers, whereas only polymers were formed from 13. In the second approach, the oxirane ring of was reduced by sodium borohydride and the resulting 6-deoxy derivative was converted into the 5-thiobenzoate; the corresponding hex-4-enofuranose was formed as a byproduct. In the third approach partial mesylation of methyl 5-thio-α-d-glucopyranoside was attempted, but the 6-mesylate 27 could be isolated only in modest yield (28%) together with rearranged 2,5-thioanhydromannofuranoside derivatives. The mechanism of this rearrangement is discussed in detail. The 6-mesylate 27 was converted via the 6-iodo derivative into the title compound.     

User−Producer Interaction in Housing Energy Innovations

Von Hippel and colleagues have highlighted the crucial role of users in innovation in different industries and types of products. They describe the innovation process in terms of the distinct domains of knowledge that producers and users possess. Producers have knowledge about technical solutions and users about their needs, the context of use, and their own capabilities as users. Both sets of knowledge are characterized by "stickiness": They move relatively freely within their own domain but are difficult to transfer outside of it.
In the case of radical innovations for sustainable consumption, the problem of "sticky information" is compounded. Both producers and consumers need to reach out of their conventional competencies and search for new solutions. "Societal actors," such as government bodies or environmental experts, can show the way to such solutions, but this new knowledge needs to be integrated with the "sticky" knowledge about everyday practices in production and consumption.
In the present article we attempt to conceptualize the role and interaction of user and producer knowledge with the knowledge of environmental experts in housing energy innovations. We do so by applying the user−producer interaction framework to a case study on the introduction of low-energy housing concepts in Finland. On the basis of this analysis, we draw conclusions on the potential and limitations of today's practices in the field. For example, we suggest that user involvement can help to enhance the acceptance of low-energy solutions but that the methods for involving users need to be adapted to the particular circumstances in each industry.     

Could 2021–2030 be the decade to couple new human values with ecological restoration? Valuable insights and actions are emerging from the Colombian Amazon

Looking ahead to the United Nations' 2021–2030 Decade of Ecosystem Restoration, we would like to ponder and discuss two fundamental goals to improve, mainstream, and scale up ecological restoration. The first is to cultivate alternative visions of the human dimension in relation to ecological restoration and other restorative activities. The second is to develop shared protocols for planning, revamping, and monitoring the progress of social goals related to ecological restoration within the social construction theoretical framework, based on three interrelated dimensions: stakeholder‐based problem definition, social representations, and legitimation. We draw on ongoing work in Caquetá (Colombian Amazonia) to consider how these dimensions may be incorporated into tangible restoration practices. Caquetá is facing the highest deforestation rates in the Amazonian region due to a highly volatile sociopolitical context and recent armed conflicts that have claimed thousands of victims to date. We conclude that the work in Caquetá demonstrates a process of social construction that effectively couples new human values with ecological restoration. Our work also provides evidence that the human dimension of restoration is a central issue in the restoration of human, social, and ecosystem health and must be integrated into the framework of the coming Decade of Ecosystem Restoration.     

Trends and inequities in colorectal cancer screening participation in Ontario,Canada, 2005–2011

Background: Participation in screening tests for colorectal cancer (CRC) is generally low in Ontario, Canada. In addition, inequities in participation exist including lower participation among low-income individuals, males and individuals living in rural areas. In April 2008, Colon Cancer Check (CCC) program, the province-wide CRC screening program, was launched in Ontario. This study describes the trends and inequities in CRC screening participation three years before and three years after the CCC, and assesses the effect of the program on CRC screening participation, overall and among certain population groups. Methods: We used administrative data to identify cohorts of individuals eligible for CRC screening in fiscal years 2005–2011. We calculated the age-standardized percent of Fecal Occult Blood Test (FOBT) participation, large bowel endoscopy participation, and being ‘up-to-date’ with CRC screening tests. Results: From 2005 to 2011, FOBT participation increased from 7.6% to 14.8%, large bowel endoscopy participation from 3.4% to 5.7%, and ‘up-to-date’ with CRC screening from 27.2% to 41.3%. Before the launch of the CCC program, the quarterly increase in FOBT participation was 0.07% (p = 0.19), increased immediately after the launch (1.8%, p < 0.01), followed by a decline (?0.08%, p = 0.08), returning to its pre-program increase rate. We noted a significant decrease in FOBT participation every summer (?0.44%, p < 0.01). The CCC program had minimal effect on large bowel endoscopy participation. Before the launch of the CCC program, the quarterly increase in ‘up-to-date’ with CRC screening was 0.9% (p < 0.01), increased immediately after the launch (2.5%, p = 0.05), followed by a modest decline thereafter (?0.59%, p < 0.02). From 2005 to 2011, recent residents living in low-income neighborhoods were consistently and significantly less likely to have a FOBT and be ‘up-to-date’ with CRC screening than long-term residents living in high-income neighborhoods (2.9–4.5%; 14.7–17.3% respectively). Pre-CCC inequities in CRC participation persisted after the launch of the program. Conclusion: CRC testing was increasing in Ontario from 2005. An immediate increase in CRC testing, FOBT in particular, occurred after the launch of the CCC program, followed by a return to its pre-CCC increase rate thereafter. Future efforts are needed to improve screening participation and address inequities.     

基于公众参与地理信息系统的广州大学城环境安全感评价研究

现有基于地点的校园环境安全研究主要以客观的案件数据为研究对象,未能揭示学生安全感与特定地点环境因素的内在联系。利用Maptionnaire问卷平台,以广州大学城为例,通过公众参与地理信息系统分析学生对校园交通、事故和人身财产方面的环境安全感评价及其空间分布。研究发现学生整体安全感评价较低,评价低的地点集中在高校周边公园绿地、城中村、体育场馆,评价高的地点主要位于高校用地范围内。结合对评价低的地点进行实地调研,基于环境设计预防犯罪（crime prevention through environmental design,简称CPTED）理论分析影响学生安全感的环境因素,针对相关问题提出对应的提升学生安全感的环境设计优化建议。     

Neighboring group participation. Part 15. Stereoselective synthesis of some steroidal tetrahydrooxazin-2-ones, as novel presumed inhibitors of human 5alpha-reductase

During the alkaline methanolysis of 3beta-acetoxy-21-chloromethyl-pregn-5-ene-20beta-N-phenylurethane, and its p-substituted phenyl derivatives, cyclization occurs, in the course of which 17beta-[3-(N-phenyl)tetrahydrooxazin-2-on-6-yl]androst-5-en-3beta-ol and its p-substituted phenyl derivatives are formed. The cyclization takes place with (N(-)-6) neighboring group participation. Oppenauer oxidation of the 3beta-hydroxy-exo-heterocyclic steroids yielded the corresponding delta4-3-ketosteroids. The structures of the new compounds were proved by IR, 1H and 13C NMR spectroscopy, using up-to-date measuring techniques such as 2D-COSY, HMQC, and HMBC. The inhibitory effects (CI50) of the delta4-3-ketosteroids on 5alpha-reductase were studied.     

Procedures and tools for generating and selecting alternatives in LCA

Life Cycle Assessments (LCAs) frequently do not contribute to sustainable development because product alternatives with a truly low environmental burden are not included in the assessment. As a result, environmentally-friendly alternatives are not uncovered, although much effort has been put into collecting inventory data and making an impact assessment. Part of this problem is caused by the defensive use of LCAs. Companies eager to show that their product is not too bad for the environment prefer to compare their product with alternatives that are not very promising in an environmental sense. To (mis)use LCAs in this way is quite easy, because the LCA methodology and handbooks provide few guidelines and little advice on how to generate and select adequate alternatives. An analysis of the problems related to the alternatives is given using insights drawn from the field of policy analysis — a field in which methodological rules for the generation of alternatives in policy studies have been developed — ecodesign and the LCA discipline, and measures to reduce the problems are developed. Explicating the different steps in the determination of alternatives in the goal and scope formulation stage of an LCA process, and the development of a toolbox for this activity, would certainly improve the quality of the selection of alternatives. Furthermore, involving stakeholders and a group of experts in the generation and selection process will increase the variety and relevance of alternatives, and the social support for alternatives.     

A simple system for monitoring biodiversity in protected areas of a developing country

The achievements of initiatives to strengthen biodiversity conservation in developing countries may be difficult to assess, since most countries have no system for monitoring biodiversity. This paper describes a simple and cost-effective, field-based biodiversity monitoring system developed specifically for areas where specialist staff is lacking. We discuss the preliminary lessons learned from protected areas in the Philippines. Whilst the monitoring system aims to identify trends in biodiversity and its uses so as to guide management action, it also promotes the participation of local people in the management, stimulates discussions about conservation amongst stakeholders and builds the capacity of park staff and communities in management skills. In addition, it seeks to provide people with direction regarding the aims of protected areas, and reinforces the consolidation of existing livelihoods through strengthening community-based resource management systems. The field methods are: (1) standardised recording of routine observations, (2) fixed point photographing, (3) line transect survey, and (4) focus group discussion. Both bio-physical and socio-economic data are used and given equal importance. The system can be sustained using locally available resources. The approach is useful in countries embarking on shared management of park resources with local communities, where rural people depend on use of natural ecosystems, and where the economic resources for park management are limited. We hope this paper will encourage other countries to develop their own biodiversity monitoring system, letting its development become a means for capacity building whilst at the same time supporting the creation of ownership.     

Solvent participation in Serratia marcescens endonuclease complexes

The monomer and dimer of the bacterium Serratia marcescens endonuclease (SMnase) are each catalytically active and the two subunits of the dimer function independently of each other. Specific interfacial waters may play a role in stability, complex formation, and functionality. We performed molecular dynamics simulations of both a subunit of SMnase and its model built complex with DNA and analyzed the relation of the hydration sites to the catalytic mechanism. It was found that the binding of DNA has little influence on the global hydration properties of the protein, including occupancy and water residence time distributions. DNA and protein recognition in our model mainly involves direct contacts by hydrogen bond and hydrophobic interactions. Water-mediated contacts exist, but are less common. Three interior water clusters were identified for SMnase. One cluster around the active site in the monomer-DNA complex shows relatively strong interactions between hydration sites as well as between the sites and the biomolecules. The simulated cluster properties agreed well with experimental data. The magnesium ion shows ligand exchange. Although Mg2+ keeps six ligands during the entire simulation, upon the binding of DNA, Asn119 loses its coordination with Mg2+, while one nonbridging oxygen of the phosphate of a DNA residue and two oxygen atoms of the side chain of Glu127 become the ligands. Waters in a nearby cluster exchange and participate in the resolvation of groups in the presence of DNA. Water thus not only participates in the cleavage of DNA but also can stabilize the transition state and the leaving groups in our model.     

A concise and practical synthesis of antigenic globotriose, alpha-D-Gal-(1-->4)-beta-D-Gal-(1-->4)-beta-D-Glc

A concise and practical synthesis of the antigenic globotriose, alpha-D-Gal-(1-->4)-beta-D-Gal-(1-->4)-beta-D-Glc (13), was achieved by coupling of a monosaccharide donor, 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-alpha-D-galactopyranosyl trichloroacetimidate (4) with a disaccharide acceptor, p-methoxyphenyl 2,3,6-tri-O-benzoyl-beta-D-galactopyranosyl-(1-->4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside (8), followed by deprotection. In spite of the existence of a C-2-ester substituent capable of neighboring-group participation in the donor, the coupling gave exclusively the alpha-linkage in satisfactory yield. The acceptor 8 was readily obtained from selective 3-O-benzoylation of the galactosyl ring of p-methoxyphenyl 2,6-di-O-benzoyl-beta-D-galactopyranosyl-(1-->4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside (7), which was prepared from p-methoxyphenyl beta-D-lactoside (5) via isopropylidenation, benzoylation, and deisopropylidenation. Donor 4 was obtained from p-methoxylphenyl 3-O-allyl-2,4,6-tri-O-benzoyl-beta-D-galactopyranoside (1) via selective 4,6-di-O-debenzoylation, oxidative removal of 1-O-MP, benzylidenation, and trichloroacetimidate formation.